Reaction apparatus for organic and/or other substances employing supercritical fluid or subcritical fluid

ABSTRACT

Disclosed is a reaction apparatus for organic and/or other substance(s) employing supercritical fluid(s) and/or subcritical fluid(s) permitting injection of organic substance(s) and/or other reactant substance(s) in homogeneous state(s) to reactor(s) without occurrence of clogging at location(s) of such injection, and also permitting actuation to occur in industrial fashion and at high energy efficiency. Reactor(s) ( 12 ) of this reaction apparatus comprise cylinder(s) ( 12   a ) and piston(s) ( 12   b ) provided at such cylinder(s) ( 12   a ). Actuation in periodic fashion is permitted by operating piston(s) ( 12   b ) to compress fluid vapor(s) and obtain supercritical fluid(s) and/or subcritical fluid(s); operating piston(s) ( 12   b ) in reverse direction(s) following conclusion of chemical reaction(s) of reactant substance(s), lowering temperature(s) and pressure(s) and stopping reaction(s); and removing, from cylinder(s) ( 12   a ), product(s) obtained while at the same time delivering new charge(s) of fluid vapor(s) to cylinder(s) ( 12   a ).

TECHNICAL FIELD

The present invention relates to a reaction apparatus for organic and/orother substances employing supercritical fluid(s) or subcriticalfluid(s). More specifically, the present invention relates to a reactionapparatus using supercritical fluid(s) and/or subcritical fluid(s) forreactive treatment or decomposition of reactant substance(s);biomass(es) and/or other such organic substance(s) and/or the like beingemployed as such reactant substance(s).

BACKGROUND ART

Conventionally proposed as physicochemical reactive decompositionmethods for biomass and other such organic substances and the like,there are—in addition to known chemical oxidation methods,photooxidation methods, combustion methods, and hydrothermalmethods—decomposition-type treatment methods employing supercriticalfluids such as are disclosed at Japanese Patent Application PublicationKokoku No. H1-38532 (1989) and so forth.

Unlike reactive hydrothermal methods employing low-temperatureconditions of 200° to 300° C. as reaction conditions, suchdecomposition-type treatment methods for organic substances and the likeemploying supercritical fluids use supercritical water at conditionsexceeding the critical pressure of 218 atmospheres and the criticaltemperature of 374° C. of water to decompose organic substances andother such reactant substances. This supercritical water possessesexcellent advantages such as the fact that the polar nature thereof canbe controlled based on temperature and pressure, permittingsolubilization of paraffinic hydrocarbons, benzene, and other suchnonpolar substances; the fact that it displays extremely excellentproperties as reaction solvent for oxidative decomposition of organicmatter in that it mixes in arbitrary ratios even with oxygen and othersuch gases, and also the fact that because it is possible to raisetemperature to the critical temperature or higher using only heat ofoxidation where the fractional carbon content of the material beingdecomposed is several percent, it is extremely excellent from a thermalenergy standpoint as well; and the fact that by using supercriticalwater it is possible through hydrolytic reaction and/or thermolyticreaction to more or less completely decompose almost any kind ofdecomposition-resistant organic matter, poisonous organic matter, or thelike.

Conventional reactive decomposition methods employing supercriticalfluids are carried out according to the following sequence. To wit,three fluids or sets of fluids—these being water including organicsubstance(s) and/or other such reactant substance(s); oxygen and/orother such oxidant fluid(s); and supercritical fluid(s)—are supplied inpreviously mixed state(s) or partially mixed state(s) to reactionvessel(s) carrying out supercritical hydration reaction(s), and thematerial in question is decomposed through oxidative process(es) underconditions which are supercritical with respect to water. By furthercausing oxidation reaction(s) to proceed, it is also possible for thematerial in question to be processed as far as carbon monoxide,hydrogen, and/or the like.

Conventional reaction apparatuses employing supercritical fluids have incommon the fact that fluid(s) are pressurized and are thereafter heated,causing fluid(s) to assume supercritical state(s) or subcriticalstate(s)—such state(s) being high-temperature, high-pressure state(s)—asa result of which reaction is made to occur. This being the case, agreat deal of energy is required when fluid(s) are made to assumehigh-temperature, high-pressure state(s).

Methods for reducing energy during pressurization in the case ofsupercritical-fluid and/or subcritical-fluid high-temperature,high-pressure fluid(s) include the development of the continuousautoclave utilizing the pipeline system (Nakamichi Yamasaki, SuinetsuKagaku Jikkensho Houkoku, Vol. 3 1-4 (1979). In this method, piston(s)and cylinder(s) are used to recover pressure from post-treatmenthigh-temperature, high-pressure fluid(s); and reduction in energy duringpressurization of unpressurized fluid(s) is achieved through use ofother piston(s) and cylinder(s) linked to piston(s) used for recovery.

For reducing energy during pressurization in the case ofsupercritical-fluid and/or subcritical-fluid high-temperature,high-pressure fluid(s), there is also the method using the apparatusdisclosed at Japanese Patent Application Publication Kokai No.H12-233127 (2000). This apparatus is provided with second drive meansaccepting the load of the driving force from first drive means employingpiston(s) within cylinder(s) to receive pressure from post-treatmenthigh-temperature, high-pressure fluid(s) and transmitting same as forceto pressurize pre-treatment fluid(s). That is, the apparatus is suchthat, after being reduced using back pressure valve(s), energy ofpost-treatment high-pressure fluid(s) is introduced into cylinder(s) atthe aforesaid first drive means. The apparatus is such that this permitsfluid(s) including reactant substance(s) to be made to assume hightemperature(s) and high pressure(s) and to be supplied in stable fashionto reaction system(s).

Furthermore, because supercritical fluid(s) and/or subcritical fluid(s)are at high temperature and high pressure, decomposition reaction(s) andso forth occurring within fluid(s) proceed extremely rapidly. For thisreason, it is necessary to employ short time(s) for treating reactantsubstance(s) with supercritical fluid(s) and/or subcritical fluid(s) andto quickly stop the rapid reactions which occur within supercriticalfluid(s) and/or within subcritical fluid(s).

Methods for shortening time for rapid treatment of reactant substance(s)with supercritical-fluid and/or subcritical-fluid high-temperature,high-pressure fluid(s) include methods employing continuous reactionapparatuses for cellulose hydrolysis (M. Sasaki, B. Kabyemela, R.Malaluan S. Hirose, N. Takeda, T. Adschiri, K. Arai; Cellulosehydrolysis in subcritical and supercritical water, J. Supercrit. Fluids1998. 13. 261-268.). This method is carried out using a flow-typereaction apparatus, treatment of reactant substance(s) being carried outaccording to the following sequence. To wit, reactant substance(s) aredirectly mixed in the vicinity of reaction vessel inlet(s) withsupercritical water which has been heated and pressurized underprescribed conditions, rapidly raising the temperature thereof untiltarget optimum reaction temperature(s) are reached. Furthermore, atreaction vessel outlet(s), rapid cooling is carried out through externalcooling by direct delivery of cold water to reaction liquid(s). In suchcase, shortening of the time for treating reactant substance(s) withsupercritical water is made possible by reducing reaction vessel volumeand/or increasing flow rate.

However, the reality at present is that there is not yet an industrialreaction apparatus for handling supercritical state(s) ofhigh-temperature, high-pressure fluid(s), such as would permit recoveryof energy as well as treatment of reactant substance(s) withsupercritical fluid(s) in extremely short period(s) of time, and such aswould also permit the aforementioned conventional reaction(s) of organicsubstance(s) and/or the like with supercritical fluid(s) to beimplemented efficiently.

With conventional reaction apparatuses for organic substance(s) and/orthe like employing supercritical fluid(s), e.g., where reactantsubstance(s) are wood meal and/or other such organic substance(s), waterunder high pressure and wherein organic substance(s) have been dispersedis rapidly heated and is maintained in supercritical and/or subcriticalstate(s) for fixed period(s) of time, hydrolytic reaction(s) occurringwhile in such supercritical and/or subcritical state(s) permittingsaccharification reaction(s) to be carried out wherein wood meal and/orother such organic substance(s) are made into glucose and/or other suchlow-molecular-weight sugar(s). In order to prevent thelow-molecular-weight saccharide(s) produced after the conclusion of suchsaccharification reaction(s) from being decomposed further, it isnecessary to rapidly cool the high-temperature supercritical waterand/or subcritical water and stop the reaction(s). Such saccharificationreaction(s) may be carried out using either a batch-type apparatus or aflow-type apparatus. Conventionally proposed reaction apparatuses, whereimplemented in the context of flow-type apparatuses, make use ofapparatus constitutions employing processes wherein realization ofhigh-temperature supercritical water state(s) occurs as a result ofmixing of low-temperature, supercritical-pressure water wherein woodmeal is dispersed with high-temperature supercritical water and causingreaction(s) to proceed, and wherein stopping of such reaction(s) iscarried out through injection of cold water therein.

However, when carrying out the aforesaid processes with suchconventional reaction apparatuses, problems such as the followingremain.

-   (1) Apparatus constitution requires pressurizing, heating, reacting,    cooling, and decompressing vessels into which water is sequentially    introduced, making apparatus constitution complicated overall.-   (2) Because time for saccharification reaction of ligneous and/or    other such organic substance(s) is short, cold water must be mixed    therewith to stop reaction. If reaction time is increased, reactant    substance(s) are overdecomposed, preventing sugars from being    obtained.-   (3) Because reaction is stopped by rapid cooling with cold water,    much water is used. For this reason, the process of concentrating    sugar(s) following reaction is made complicated.-   (4) The fact that the cooling process is carried out using cold    water means that energy consumption is high.-   (5) It is difficult to achieve distribution in such state that    ligneous and/or other such organic substance(s) are uniformly    dispersed in water at high pressure.

It is therefore an object of the present invention to provide a reactionapparatus for organic and/or other substance(s) employing supercriticalfluid(s) and/or subcritical fluid(s) permitting injection of organicsubstance(s) and/or other reactant substance(s) in homogeneous state(s)to reactor(s) and permitting treatment of reactant substance(s) withsupercritical fluid(s) to occur in extremely brief period(s) of time,and also permitting actuation to occur in industrial fashion and at highenergy efficiency.

DISCLOSURE OF INVENTION

In order to achieve the aforesaid object(s), a reaction apparatus fororganic and/or other substance(s) employing supercritical fluid(s)and/or subcritical fluid(s) in accordance with the present invention ischaracterized in that means for compressing vapor(s) and obtainingsupercritical fluid(s) and/or subcritical fluid(s), means for bringingsuch supercritical fluid(s) and/or subcritical fluid(s) into contactwith organic matter and/or other reactant substance(s) and causingoccurrence of chemical reaction(s), and means for causing expansion anddecompression of fluid(s) including product(s) produced as a result ofsuch chemical reaction(s) comprise cylinder(s) and piston(s) provided atsuch cylinder(s), the reaction apparatus being made to actuate inperiodic fashion by actuating such piston(s) to cause compression offluid(s); actuating piston(s) in reverse direction(s) following chemicalreaction(s) involving reactant substance(s) and lowering temperature(s)and pressure(s); and removing, from cylinder(s), fluid(s) includingproduct(s) obtained and delivering new charge(s) of vapor(s) tocylinder(s).

Here, the aforesaid cylinder(s) and piston(s) are reciprocating-typereactor(s), and from a functional standpoint, are of the exact samephysical type as plunger-type apparatuses wherein plunger(s) engage inreciprocating motion within cylinder(s). Reaction apparatus(es) inaccordance with the present invention are such that pressurization,heating, reaction, cooling, and decompression take place within the samecylinder(s) as a result of operation of piston(s) at cylinder(s). Thisbeing the case, simplification of the reaction apparatus is madepossible.

A reaction apparatus in accordance with the present invention employspiston(s) to adiabaticly compress vapor(s) introduced into cylinder(s)and attain supercritical and/or subcritical state(s) of fluid(s).Thereafter, piston(s) are again driven, adiabatic expansion of fluid(s)causing cooling of supercritical and/or subcritical state(s) of suchfluid(s). At such time, by converting vertical motion of piston(s) intorotary motion or the like and adjusting speed(s) thereof, it is possibleto suppress overdecomposition of reactant substance(s) with a“resolution” which is such that reaction(s) occurring in supercriticaland/or subcritical fluid(s) are divided into extremely brief period(s)of time, and to quickly stop (freeze) reaction(s) without admixture oflow-temperature liquid(s) (cold water in the case where the fluid iswater) therewith. As a result, because low-temperature fluid(s) are notused, concentration(s) of sugar(s) and/or the like which constitute theproduct(s) obtained can be maintained at high levels.

Moreover, converting the work represented by adiabatic expansion atpiston(s) into rotary motion or the like permits same to be reused aswork for adiabatic compression, permitting treatment with littleconsumption of energy even where reaction(s) of substance(s) beingtreated must be controlled with a “resolution” which is divided intoextremely brief period(s) of time on the order of seconds or less.

Supercritical-fluid temperature and pressure conditions realized insidethe apparatus of the present invention may be freely controlled based onfluid compression ratio(s), temperature(s) of saturated vapor(s)introduced thereinto, and amount(s) of liquid(s) (water in the casewhere the fluid is water) added. In addition, because introduction ofsubstance(s) being treated into reactor(s) is carried out usingnozzle(s) to spray same at high pressure together with liquid(s) atstage(s) where saturated vapor(s) of fluid(s) are introduced intocylinder(s) and/or during mid-compression of vapor(s), introduction canbe carried out such that substance(s) being treated are homogeneouslydispersed in reactor(s).

In reaction apparatus(es) in accordance with the present invention, asexamples of fluids which may attain supercritical state(s)—in additionto water—carbon dioxide, nitrous oxide, Freon 12, Freon 13, ethane,ethylene, propane, propylene, butane, hexane, methanol, ethanol,benzene, toluene, ammonia—and a wide variety of other substances inaddition thereto—may be cited.

Vapor(s) in reaction apparatus(es) in accordance with the presentinvention may be vapor(s) of any of the aforesaid varieties of fluids,and may be obtained using boiler(s) or the like. Compressive actionoccurring within reactor(s) into which such fluid vapor(s) have beenintroduced causes same to assume supercritical state(s). Suchcompression causes high-temperature, high-pressure fluid(s) in targetsupercritical and/or subcritical state(s) to be produced in shortperiod(s) of time when piston(s) are near top dead center. Contactbetween such high-temperature, high-pressure fluid(s) and reactantsubstance(s) causes hydrolytic reaction(s) and/or the like to occur atreactant substance(s), and this permits reactant substance(s) to bedecomposed and/or the like.

While the time during which high-temperature, high-pressure fluid(s) insupercritical and/or subcritical state(s) and reactant substance(s) mustbe in contact for such reaction(s) to occur varies with temperature(s)and pressure(s) reached by fluid(s), this will often be an extremelybrief period of time anywhere from several minutes to several seconds orless. In reaction apparatus(es) in accordance with the presentinvention, temperature(s) and pressure(s) of target [value(s)] orgreater might for example be attained for approximately 1/20th of thestroke(s) of the piston(s) in the reactor(s), and if dwell time(s)thereat were to be made to be 0.01 sec this would work out to beapproximately 300 rpm. Because this is a rotational velocity more thancapable of being realized by an engine of identical composition, it ismore than possible to realize treatment times on the order of seconds orless. Furthermore, through repeated reaction of the same reactantmaterial it is also more than possible to realize reactions occurring onthe order of several minutes.

Supercritical conditions for fluid(s) in reaction apparatus(es) inaccordance with the present invention include supercritical fluid(s) andsubcritical fluid(s). For example, while both the temperature and thepressure of a supercritical fluid might be in supercritical states, thetemperature or the pressure of a subcritical fluid might be atsupercritical conditions, which would mean that conditions are calmerthan supercritical conditions. Accordingly, with respect to reactionconditions, selection of supercritical fluid(s) and subcriticalconditions should be carried out as appropriate based on type(s) ofreactant substance(s), type(s) of reaction product(s), and so forth.

As stated above, high-temperature, high-pressure fluid(s) at reactor(s)in reaction apparatus(es) in accordance with the present invention arethereafter rapidly cooled by rapid expansion of cylinder volume(s) orthe like due to piston(s) or the like. This rapid cooling causeschemical reaction(s) of reactant substance(s) to be frozen (forciblystopped). This freezing of reaction(s) may be carried out in extremelybrief period(s) of time, as was the case with the aforesaid compressionprocess(es). Product(s) are moreover discharged from reactor interior(s)together with vapor(s) when piston(s) are near bottom dead center.

Reaction apparatus(es) in accordance with the present invention may beconstituted such that driving of piston(s) causes vapor(s) to becompressed at only one side within cylinder(s).

Reaction apparatuses for organic and/or other substance(s) employingsupercritical fluid(s) and/or subcritical fluid(s) in accordance withthe present invention include constitutions wherein delivery of newcharge(s) of vapor(s) to cylinder(s) only involves saturated vapor(s),saturated fluid liquid(s) or cold fluid(s) being injected intocylinder(s) together with reactant substance(s) during initiation ofcompression by piston(s), in mid-compression, or following conclusion ofcompression.

Reaction apparatuses for organic and/or other substance(s) employingsupercritical fluid(s) and/or subcritical fluid(s) in accordance withthe present invention include constitutions wherein volume(s), at whichvapor compression is carried out, formed by piston(s) and cylinder(s)are provided to either side of piston(s), and/or constitutions whereincompressor-expander(s) is or are provided to either side of piston(s),with injector(s) (feedstock spray apparatus(es)) being provided at eachthereof.

Reaction apparatuses for organic and/or other substance(s) employingsupercritical fluid(s) and/or subcritical fluid(s) in accordance withthe present invention include constitutions wherein wet vapor(s) arecompressed by one of volumes or sets of volumes, at which compression ofvapor(s) is carried out, formed by piston(s) and cylinder(s) andprovided to either side of piston(s), the other of volumes or sets ofvolumes being maintained at high pressure(s).

Reaction apparatuses for organic and/or other substance(s) employingsupercritical fluid(s) and/or subcritical fluid(s) in accordance withthe present invention include constitutions wherein, at mechanism(s)comprising cylinder(s) and piston(s) provided at such cylinder(s), workof piston(s) is recovered. Recovery of work of piston(s) makes itpossible to drive reactor(s) with high energy efficiency.

Reaction apparatus(es) for organic and/or other substance(s) employingsupercritical fluid(s) and/or subcritical fluid(s) in accordance withthe present invention include constitutions wherein means forcompressing vapor(s) and obtaining supercritical fluid(s) and/orsubcritical fluid(s), means for bringing supercritical fluid(s) and/orsubcritical fluid(s) into contact with organic matter and/or otherreactant substance(s) and causing occurrence of chemical reaction(s),and means for causing expansion and decompression of fluid(s) includingproduct(s) produced as a result of chemical reaction(s) comprise rotorchamber(s) and rotor(s) provided at such rotor chamber(s), the reactionapparatus being made to actuate in periodic fashion by rotating suchrotor(s) within rotor chamber(s) to cause compression of vapor(s);further rotating rotor(s) following the aforesaid chemical reaction(s)and lowering temperature(s) and pressure(s), and removing, from rotorchamber(s), fluid gas(es) and/or liquid(s) including product(s) obtainedand delivering new charge(s) of vapor(s) to rotor chamber(s).

Compared with reciprocating mechanism(s) comprising cylinder(s) andpiston(s) provided at such cylinder(s), rotary mechanism(s) comprisingrotor chamber(s) and rotor(s) provided at such rotor chamber(s) possessthe advantage that compression and expansion of substance(s) to betreated which are introduced into rotor chamber(s) can be carried outmore rapidly, as well as the fact that reductions in size and weight canbe achieved.

Reaction apparatuses for organic and/or other substance(s) employingsupercritical fluid(s) and/or subcritical fluid(s) in accordance withthe present invention include constitutions wherein means forcompressing vapor(s) and obtaining supercritical fluid(s) and/orsubcritical fluid(s), means for bringing supercritical fluid(s) and/orsubcritical fluid(s) into contact with organic matter and/or otherreactant substance(s) and causing occurrence of chemical reaction(s),and means for causing expansion and decompression of fluid(s) includingproduct(s) produced as a result of chemical reaction(s) compriseturbocompressor(s) and turbine(s) directly coupled to suchturbocompressor(s); operation of turbocompressor(s) causing compressionof vapor(s), temperature(s) and pressure(s) being lowered by way ofturbine(s) following conclusion of chemical reaction(s), and motiveforce(s) being recovered as a result of direct coupling ofturbocompressor(s) and turbine(s) extracting therefrom fluid(s)including product(s) obtained. Such constitutions are for continuousreaction of reactant substance(s).

Reaction apparatuses for organic and/or other substance(s) employingsupercritical fluid(s) and/or subcritical fluid(s) in accordance withthe present invention include constitutions provided with means forcausing fluid(s) including product(s) obtained from reaction(s) to beseparated into saturated fluid(s) and saturated vapor fluid(s) bycyclone separator(s) and/or centrifugal separator(s).

Included among reaction apparatuses for organic and/or othersubstance(s) employing supercritical fluid(s) and/or subcriticalfluid(s) in accordance with the present invention there areconstitutions provided with explosive disintegration apparatus(es) thatrapidly depressurize reactant substance(s) while same is or are immersedin high-pressure saturated fluid(s); reactant substance(s) beingpulverized by such explosive disintegration apparatus(es). This is formaking it possible, through pulverization, to easily and quicklyintroduce reactant substance(s) into the reaction apparatus of thepresent invention.

Included among reaction apparatuses for organic and/or othersubstance(s) employing supercritical fluid(s) and/or subcriticalfluid(s) in accordance with the present invention are constitutionswherein passage switching valve(s) and/or other such open-/close-typemember(s) are respectively provided at introductive port(s) andscavenging valves(s) in mechanism(s) comprising cylinder(s), rotorchamber(s), and/or turbocompressor(s) and piston(s) for suchcylinder(s), rotor(s) for such rotor chamber(s), and/or turbine(s) forsuch turbocompressor(s); such open-/close-type member(s) being such asto allow setting of open and/or closed time(s) thereof, and setting ofsuch open-/close-type member(s) so as to cause closure thereof for fixedperiod(s) of time permitting supercritical treatment at suchmechanism(s) to be carried out continuously and in ongoing fashion.

Setting of respective open-/close-type member(s) at such mechanism(s) soas to cause closure thereof for fixed period(s) of time makes itpossible to cause reaction of organic and/or other substance(s) bysupercritical fluid(s) and/or subcritical fluid(s) to be carried outcontinuously and repeatedly at the same mechanism(s), as a result ofwhich it is possible to react to completion those substance(s) beingtreated which require long times.

Reaction apparatuses for organic and/or other substance(s) employingsupercritical fluid(s) and/or subcritical fluid(s) in accordance withthe present invention include constitutions wherein mechanism(s)comprising cylinder(s), rotor chamber(s), and/or turbocompressor(s) andpiston(s), rotor(s), and/or turbine(s) for same are such that aplurality thereof are provided. Ways of increasing reaction yield(s) ofreaction(s) include, in addition to formation of multiple banks ofcylinders and/or the like, provision of a plurality of such mechanisms.

In the case of the foregoing latter constitution, this may beconstituted such that scavenger member(s) and member(s) introducingvapor(s) into respective cylinder(s), respective rotor chamber(s),and/or respective turbocompressor(s) in mechanism(s) comprisingcylinder(s), rotor chamber(s), and/or turbocompressor(s) and piston(s),rotor(s), and/or turbine(s) for same, there being a plurality thereof,are sequentially coupled by way of passage coupling valve(s) and/orother such open-/close-type member(s); permitting respective processesperformed by means for compressing vapor(s) and obtaining supercriticalfluid(s) and/or subcritical fluid(s), means for bringing supercriticalfluid(s) and/or subcritical fluid(s) into contact with organic matterand/or other reactant substance(s) and causing occurrence of chemicalreaction(s), and means for causing expansion and decompression offluid(s) including product(s) produced as a result of chemicalreaction(s) to be carried out a plurality of times. This is for, wherereactant substance(s) are to undergo supercritical treatment for longtimes on the order of minutes, opening the aforesaid open-/close-typemember(s) as needed and causing supercritical treatment in accordancewith the present invention to be carried out repeatedly andcontinuously.

Reaction apparatuses for organic and/or other substance(s) employingsupercritical fluid(s) and/or subcritical fluid(s) in accordance withthe present invention include constitutions provided withoxidant-introducing apparatus(es) permitting introduction of oxidant(s)into cylinder(s), rotor chamber(s), and/or turbocompressor(s);introduced organic matter and/or other reactant substance(s) beingoxidatively decomposed while in supercritical and/or subcriticalstate(s).

Moreover, reaction apparatuses for organic and/or other substance(s)employing supercritical fluid(s) and/or subcritical fluid(s) inaccordance with the present invention include constitutions providedwith gasification apparatus(es) further separating, into gascomponent(s) and vapor component(s), saturated vapor(s) separated fromfluid(s) including product(s).

Included among reaction apparatuses for organic and/or othersubstance(s) employing supercritical fluid(s) and/or subcriticalfluid(s) in accordance with the present invention are constitutionsprovided with ethanol fermentor(s) having yeast(s), colon bacillus orbacilli, and/or other such microorganism(s) into which, where product(s)are glucose and/or other such low-molecular-weight sugar(s) and/or thelike obtained from decomposition of biomass(es) and same is or areintroduced thereinto; sugar substrate(s) introduced into ethanolfermentor(s) being converted as far as ethanol by the aforesaidmicroorganism(s).

Furthermore, included among reaction apparatuses for organic and/orother substance(s) employing supercritical fluid(s) and/or subcriticalfluid(s) in accordance with the present invention are constitutionsprovided with ABE fermentor(s) having ABE fermentation microorganism(s)into which, where product(s) are low-molecular-weight sugar(s) and/orthe like obtained from decomposition of biomass(es) and same is or areintroduced thereinto; sugar substrate(s) introduced into ABEfermentor(s) being decomposed as far as acetone, butanol, and ethanol byABE fermentation microorganism(s). With ABE fermentor(s), in comparisonwith the aforesaid conventional methods, ethanol and/or other suchlow-molecular-weight sugar(s) and/or other such substrate(s) produced asa result of contact with supercritical fluid(s) can be broken down intolower-molecular-weight molecule(s) and solubilized in fluid(s) moreefficiently and with less consumption of energy; and moreover, ABEfermentation microorganism(s) permit treatment to be carried out suchthat conversion proceeds as far as acetone, butanol, and ethanol.

Included among reaction apparatuses for organic and/or othersubstance(s) employing supercritical fluid(s) and/or subcriticalfluid(s) in accordance with the present invention are constitutionsprovided with methane fermentor(s) having methane fermentationmicroorganism(s) into which, where product(s) are low-molecular-weightproduct component(s) obtained from decomposition of biomass(es) and sameis or are introduced thereinto; substrate(s) broken down intolower-molecular-weight molecule(s) which are introduced into methanefermentor(s) being converted as far as methane gas by methanefermentation microorganism(s). With methane fermentor(s), in comparisonwith the aforesaid conventional methods, biomass(es) can be broken downinto lower-molecular-weight molecule(s) and solubilized in fluid(s) as aresult of contact with supercritical fluid(s) more efficiently and withless consumption of energy; and moreover, methane microorganism(s)permit conversion to proceed as far as methane gas.

Reaction apparatus(es) for organic and/or other substance(s) employingsupercritical fluid(s) and/or subcritical fluid(s) in accordance withthe present invention permit decomposition treatment where biomassfeedstock(s) including municipal refuse is or are employed as reactantsubstance(s). That is, this is the case where reactant substance(s) aresugar(s) obtained as a result of decomposition of biomass(es). This isthe case where reactant substance(s) is or are any substance(s) selectedfrom among biomass feedstock(s) including municipal refuse, discardedtire(s), coal and/or other such carbon-containing substance(s); andproduct(s) is or are synthesized gas(es) including methane gas,hydrogen, carbon dioxide, and carbon monoxide obtainable throughdecomposition of the aforesaid selected substance(s). This is the casein constitutions wherein reactant substance(s) is or are PET bottle(s)and/or other such high-molecular-weight polymer(s), and product(s) is orare high-molecular-weight-polymer-material feedstock substance(s); thisis the case where reactant substance(s) is or are PCB(s), R-seriesrefrigerant(s), DXN(s) (dioxin(s)), and/or other such substance(s)having decomposition-resistant content, and reactant substance(s) is orare decomposed and rendered harmless; and this is the case wherereactant substance(s) is or are waste cooking oil(s) and/or other suchfat(s) and/or oil(s) which is or are converted into fatty acid ester(s)by supercritical fluid(s) and/or subcritical fluid(s).

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a flowchart of a reaction apparatus for organic and/or othersubstances employing supercritical fluid(s) and/or subcritical fluid(s)in accordance with the present invention.

FIG. 2 is a partial flowchart in a situation where cam-type actuationmechanism(s) are employed at reactor(s) in a reaction apparatus fororganic and/or other substances employing supercritical fluid(s) and/orsubcritical fluid(s) in accordance with the present invention.

FIG. 3 is a partial flowchart in a situation where rotary-typecompressor-expander(s) are used instead of reciprocating-typecompressor-expander(s) in a reaction apparatus for organic and/or othersubstances employing supercritical fluid(s) and/or subcritical fluid(s)in accordance with the present invention.

FIG. 4 is a flowchart in a situation where turbo-typecompressor-expander(s) are used in a reaction apparatus for organicand/or other substances employing supercritical fluid(s) and/orsubcritical fluid(s) in accordance with the present invention.

FIG. 5 is a flowchart in a situation where turbo-typecompressor-expander(s) are used in a reaction apparatus for organicand/or other substances employing supercritical fluid(s) and/orsubcritical fluid(s) in accordance with the present invention.

FIG. 6 is a flowchart of another embodiment of a reaction apparatus fororganic and/or other substances employing supercritical fluid(s) and/orsubcritical fluid(s) in accordance with the present invention.

FIG. 7 is a flowchart of another embodiment of a reaction apparatus fororganic and/or other substances employing supercritical fluid(s) and/orsubcritical fluid(s) in accordance with the present invention.

FIG. 8 is a partial flowchart illustrating an embodiment in which areaction apparatus for organic and/or other substances employingsupercritical fluid(s) and/or subcritical fluid(s) in accordance withthe present invention is used to cause reactant substance(s) to undergocontinuous and repeated treatment.

FIG. 9 is a partial flowchart illustrating an embodiment in which, in areaction apparatus for organic and/or other substances employingsupercritical fluid(s) and/or subcritical fluid(s) in accordance withthe present invention, a plurality of reactors are provided therein.

FIG. 10 is a partial flowchart illustrating an embodiment in whichoxidant supply apparatus(es) is or are provided at a reaction apparatusfor organic and/or other substances employing supercritical fluid(s)and/or subcritical fluid(s) in accordance with the present invention.

FIG. 11 is a partial flowchart illustrating an embodiment in whichgasification treatment apparatus(es) is or are provided at a reactionapparatus for organic and/or other substances employing supercriticalfluid(s) and/or subcritical fluid(s) in accordance with the presentinvention.

FIG. 12 is a partial flowchart illustrating an embodiment in whichethanol fermentation apparatus(es) is or are provided at a reactionapparatus for organic and/or other substances employing supercriticalfluid(s) and/or subcritical fluid(s) in accordance with the presentinvention.

FIG. 13 is a partial flowchart illustrating an embodiment in which ABEfermentation apparatus(es) is or are provided at a reaction apparatusfor organic and/or other substances employing supercritical fluid(s)and/or subcritical fluid(s) in accordance with the present invention.

FIG. 14 is a partial flowchart illustrating an embodiment in whichmethane gas fermentation apparatus(es) is or are provided at a reactionapparatus for organic and/or other substances employing supercriticalfluid(s) and/or subcritical fluid(s) in accordance with the presentinvention.

FIG. 15 is a drawing illustrating work cycles in a flow-typesupercritical-fluid and/or subcritical-fluid reaction apparatuspresented as a comparative example.

FIG. 16 is a drawing showing specific enthalpy during processesoccurring at a flow-type supercritical-fluid and/or subcritical-fluidreaction apparatus presented as a comparative example.

FIG. 17 is a drawing showing specific enthalpy during processesoccurring at a reaction apparatus for organic and/or other substancesemploying supercritical fluid(s) and/or subcritical fluid(s) associatedwith the present invention.

FIG. 18 is a drawing showing values for compression ratio ε calculatedfor a situation where the pressure of the wet vapor prior to compressionis 3 MPa and for the state existing at the target point when the fluidmedium is water.

FIG. 19 is a drawing showing critical conditions for various fluidmedia.

FIG. 20 is a drawing showing values for compression ratio ε calculatedfor a situation where the pressure of the wet vapor prior to compressionis 3 MPa and for the state existing at the target point when the fluidmedium is Freon 12.

BEST MODE OF CARRYING OUT INVENTION

Next, best mode(s) of carrying out the present invention are describedwith reference to the drawings. Reaction apparatus 10 for organic and/orother substances employing supercritical fluid(s) and/or subcriticalfluid(s) and shown in FIG. 1 uses water as fluid medium. Reactionapparatus 10 has as its basic component reciprocating-type reactor 12which is made up of boiler 11 for obtaining vapor from water; means forcompressing this vapor and obtaining supercritical water and/orsubcritical water; means for bringing this supercritical water and/orsubcritical water into contact with organic matter and/or other reactantsubstance(s) and causing occurrence of chemical reaction(s); and meansfor causing expansion and decompression of water including product(s)produced as a result of such chemical reaction(s).

Boiler 11 is employed to obtain vapor from water. Fuel C is supplied toboiler 11 from pump 27, while at the same time, air D is suppliedthereto by blower 28. This water vapor is introduced into reactor 12.

At reactor 12, water vapor from water may be compressed. That is,reactor 12 is a high-pressure compressor-expander comprising cylinder 12a and piston 12 b provided at such cylinder 12 a. Provided to eitherside of piston 12 b are volumes 12A and 12B. Piston 12 b is actuated bymeans of crank mechanism 13 and water vapor is compressed at volume 12A,permitting formation of supercritical water and/or subcritical water. Inaddition, this supercritical water and/or subcritical water is broughtinto contact with wood meal serving as reactant substance, making itpossible to cause wood meal to be made to undergo hydrolyticreaction(s). Note that crank mechanism 13 may also be a cam mechanism.

This wood meal is such that ligneous chips A are explosivelydisintegrated by explosive disintegrator 15, pulverizing wood meal. Thiswood meal is introduced into rotary feeder 14, while at the same time,water B is delivered to rotary feeder 14 in a pressurized state by meansof a pump. As wood meal diffuses throughout water at rotary feeder 14,wood meal is supplied to reactor 12 in sprayed state by means ofinjector 14 a. The finer the wood meal the better, since this willpermit facilitation of chemical reaction(s) and prevention of spraynozzle clogging. Accordingly, circumstances will be all the morefavorable if wood meal is pulverized by explosive disintegration andthis is furthermore made into a slurry.

The aforesaid hydrolytic reaction(s) of wood meal may be made to occurwhen piston 12 b is in the vicinity of top dead center. Followingconclusion of hydrolytic reaction(s) of wood meal, piston 12 b may beactuated, causing expansion of vapor within cylinder 12 a and causingsame to once again become wet vapor, and also causing termination ofsuch reaction(s) due to the decrease in temperature at such time.

Such reaction processes require neither high-temperature water norcooling water; and furthermore, because wood meal reaction time [can be]varied by changing actuation velocity of piston 12 b, control thereof iseasy. Furthermore, at reactor 12, while a large amount of work isrequired during compression by piston 12 b, operations are carried outso as to cause this work to be extracted during expansion such thatcancellation occurs. In such case, because mixture and thermal transferare not based on processes accompanied by loss of energy, the net workrequired is only the energy consumed during chemical reaction(s), thefrictional energy at piston 12 b, and various other small amounts ofenergy such as that of the pump(s) and so forth. Accordingly, actuationcan be carried out with high energy efficiency.

Descension of piston 12 b causes port 12 c to open at appropriatetime(s), actuation being made to occur so as to expel reaction productstogether with wet vapor. Such operation of reactor 12 permits actuationto occur in the context of two-cycle and/or four-cycle mechanism(s). Forexample, because it is alright if scavenging is somewhat incomplete,uniflow-type two-cycle device(s) may be used as reactor 12. In suchcase, at cylinder 12 a, port 12 e might be opened by piston 12 b whenexpansion is concluded, introducing a new charge of vapor, and usedvapor might be discharged from valve 12 c on the opposite sidetherefrom.

Delivery of new charges of vapor to chamber 12A of cylinder 12 a mightonly involve saturated vapor; it being possible for saturated liquid orcold water to be injected into compressor-expander 12 together with woodmeal during initiation of compression by piston 12 b, inmid-compression, or following conclusion of compression. Saturated vaporat such time might be such that obtained from boiler 11 is supplied tothe interior of cylinder 12 a.

The liquid fraction at boiler 11, i.e., cold water, might be sprayedinto cylinder 12 a simultaneous with supply of saturated vapor toreactor 12 or during the course of compression, permitting adjustment ofthe dryness of the vapor within cylinder 12 a. If this vapor drynessshould become too low, it is because the amount of cooling water beingsprayed is too small.

Injection into cylinder 12 a might be carried out such that a fixedamount of wood meal is in a homogeneously dispersed state within thejetted stream at the time of such spraying of cold water. Because finewood meal can be dispersed in this spray due to the fact that cold watercan be sprayed at high velocity, and because wood meal can be propelledwith saturated liquid, it is possible to prevent occurrence of cloggingof spray nozzle(s). Furthermore, the reason that cold water is used forspraying is to impart wood meal with the required wetness, and also toprevent thermal decomposition of wood meal within cylinder 12 a bymaintaining the wood meal at low temperature (150° C. or lower beingpreferred).

Included among reaction apparatuses in accordance with the presentinvention there are, moreover, constitutions provided with means forcausing water including product(s) obtained from chemical reaction(s) tobe separated into saturated water and saturated vapor by cycloneseparator(s) 23 (and/or centrifugal separator(s)).

That is, low-pressure wet vapor discharged from cylinder 12 a isdelivered to cyclone separator 23, and water including products obtainedas a result of chemical reaction is separated into saturated water andsaturated vapor. At such time, low-pressure saturated vapor produced asa result of separation by cyclone separator 23 might be such that aportion of the heated vapor is guided to motive force generator 17 whichis separately provided with flow rate adjustment valve (gauge) 31,permitting the energy therefrom to be used as motive force at reactor 12to which cylinder 12 a and piston 12 b belong. 13 is a crank mechanismcoupled to the end of the shaft of piston 12 b; 16 is a crank mechanismfor motive force generator 17; and 21 a through 21 d are heatexchangers. As a result hereof, overall energy efficiency of reactionapparatus 10 can be increased. Vapor used by motive force generator 17can be condensed by condenser 18 and returned by way of filter 19 aswater for supply to boiler 11.

In order to use energy from the aforesaid motive force generator 17 asmotive force for reactor 12, crank mechanism 13 and crank mechanism 16are coupled together. That is, motive force from motive force generator17 is converted into rotary motion and is transmitted from crankmechanism 16 to crank mechanism 13, and this rotary motion is used asmotive force for piston 12 b at reactor 12.

In such case, either or both of crank mechanisms 13 and 16 may beconstituted from cam mechanism(s). FIG. 2 shows a constitution employingcam mechanism 130 in place of crank mechanism 13. Cam mechanism 130comprises cam 130 a and cam base 130 b, and cam 130 a abuts end region120 c of piston 120 b at reactor 120A, permitting rotary motion of cam130 to be converted into extensile motion of piston 120 b. 120 a is acylinder.

Reaction products from cyclone separator 23 are concentrated, and arethereafter introduced into gas-liquid separator 26 and are separatedinto saturated vapor and saturated water. The reason that separationinto saturated vapor and saturated water is carried out here is becauseit is expected that reaction products will be contained only within theliquid and not within the vapor. Accordingly, concentration of reactionproducts may be accomplished merely by further separating the heatedvapor of that liquid therefrom. This makes it possible to simplify theprocedure for concentrating the reaction products which are obtained.Furthermore, because reaction products are not included within saturatedvapor, same may be returned to boiler 11 by means of pump 20 or may besent to motive force recovery apparatus 17 and used as source of motiveforce in the same manner as described above.

FIG. 3 shows a constitution in which rotary-type reactor 120B is used inplace of the aforesaid reactor 12. Reactor 120B comprises rotor chamber120 d and its rotor 120 e. Rotor 120 e rotates elliptically in suchfashion that the outside circumferential surface thereof is inscribed byrotor chamber 120 d. Furthermore, drive shaft 120 f is coupled by gearat the inside circumferential region of rotor 120 e, rotation of driveshaft 120 f causing rotor 120 e to rotate elliptical fashion. Othercomponents are as described above.

At reactor 120B, elliptical rotation of rotor 120 e causes water vaporfrom boiler 11 to be captured into rotor chamber 120 d from vaporintroduction hole 120 g and to be compressed, as a result of whichsupercritical water and/or subcritical water is or are formed. Thissupercritical water and/or subcritical water and wood meal jetted fromfeeder 14 b of rotary feeder 14 come into contact, and wood meal isdecomposed by hydrolytic reaction(s). Thereafter, at rotor chamber 120d, rotor 120 e may be rotated, expansion causing the vapor therein toonce again become wet vapor, and also causing termination of chemicalreaction(s) of wood meal due to the decrease in temperature at suchtime.

At such reaction processes, the fact that neither high-temperature waternor cooling water is required, and the fact that wood meal hydrolysisreaction rate can be easily controlled based on rotational velocity ofrotor 120 e, are the same as was the case at the aforesaid reactor 12.

At reactor 120B, low-pressure wet vapor may be discharged from dischargehole 120 h of rotor chamber 120 d as rotor 120 e rotates. Moreover, thisdischarged low-pressure wet vapor may be delivered to cyclone separator23, and water including products obtained as a result of chemicalreaction may be separated into saturated water and saturated vapor.Moreover, rotary operation of rotor 120 e may be directly extracted asmotive force for drive shaft 120 f, and this motive force may be onceagain used for rotary operation of rotor 120 e and/or the like.Accordingly, treatment can be carried out with high energy efficiency.On this score as well, action in the present embodiment is the same asthe action described above for reactor 12.

Next, the reactor shown in FIG. 4 is a turbo-type high-pressurecompressor-expander, water vapor from boiler 11 being introduced intocentrifugal compressor 34, which represents one type of turbocompressor.At centrifugal compressor 34, water vapor introduced thereinto may becompressed to form supercritical water and/or subcritical water. Inaddition, this supercritical water and/or subcritical water is deliveredto high-pressure reactor 33.

At high-pressure reactor 33, ligneous feedstock A is introduced intoligneous slurry tank 41, and after this is mixed homogeneously withwater, the mixture is continuously supplied therefrom by means of a feedpump. This wood meal which serves as reactant substance comes intocontact with supercritical water and/or subcritical water delivered tothat high-pressure reactor 33 and undergoes hydrolytic reaction(s).

Chemical reaction of this wood meal is such that supercritical waterand/or subcritical water may be introduced into radial turbine 35 fromhigh-pressure reactor 33, resulting in expansion and causing the vaportherein to once again become wet vapor, and also causing termination ofsuch reaction(s) due to the decrease in temperature at such time 36 is amotor for driving radial turbine 35.

Such reaction processes require neither high-temperature water norcooling water; and furthermore, because wood meal reaction time can bevaried by changing rotational velocity of radial turbine 35, controlthereof is easy. Furthermore, at centrifugal separator 34, while a largeamount of work is required, actuation is carried out so as to cause thiswork to be extracted such that cancellation occurs during expansion byradial turbine 35 which is arranged along a single axis. Vapor which hasexited turbine 35 undergoes gas-liquid separation at cyclone separator23, and while most of the saturated vapor is returned to boiler 11, aportion thereof is guided to radial turbine 37, producing motive forceand allowing electrical power to be obtained from electrical generator38, with this being used to supplement driving of centrifugal compressor34.

As shown in FIG. 5, in order to easily obtained high-temperature,high-pressure state(s) of fluid(s), two stages of, or a plurality ofstages of, centrifugal compressors 34 and radial turbines 35 may beinstalled. In such a case, mixer(s) 37 is or are installed between thetwo stages of centrifugal separators 38, and cold water is supplied byfeed pump 41 to carry out adjustment of wetness of heated vapor.

Next, as shown in FIG. 6, reaction apparatus(es) in accordance with thepresent invention include constitutions wherein volumes are provided toeither side of piston 12 b, vapor passing through one of the volumesbefore being introduced into the other of the volumes, and compressionof vapor being carried out at only the one thereof. Because suchconstitution permits reduction in the pressure difference between thevolumes to either side thereof, it is possible to reduce the load on thebearing at 13.

At the reaction apparatus in accordance with the present invention shownin FIG. 7, reaction apparatus 12 includes a constitution wherein volumeswhich are formed by cylinder 12 a and piston 12 b and at whichcompression of vapor is carried out are provided to either side ofpiston 12 b. Adoption of such a multiple-acting constitution makes itpossible to increase the amount of reactant substance(s) undergoingchemical reaction per unit time.

The reaction apparatus in accordance with the present invention shown inFIG. 8 is constituted such that passage switching valves 12 g, 12 h arecoupled to scavenging valve 12 c and introductive port 12 e in amechanism at reactor 12 comprising cylinder 12 a and piston 12 bbelonging to this cylinder 12 a. Because during a time when both ofpassage switching valves 12 g, 12 h are closed the passages atscavenging valve 12 c and introductive port 12 e will be closed off, itis possible to set the apparatus so as to cause reactant substance(s) toundergo treatment by supercritical fluid(s) within this reactor 12continuously and repeatedly for a fixed period of time.

In this reaction apparatus, when passage switching valves 12 g, 12 h areclosed, discharge of product from scavenging valve 12 c is stopped andinflow of new charge(s) of vapor from introductive port 12 e is alsostopped. This being the case, at reactor 12, supercritical treatment ofreactant substance(s) is continuously and repeatedly carried out aplurality of times by piston 12 b. This makes it possible to achieverequired reaction time in accordance with the type of reactantsubstance, making it possible to efficiently treat the entirety of thereactant substance even in situations where long times on the order ofminutes or the like are required in order for the reaction(s) to besatisfactorily completed.

As shown in FIG. 9, reaction apparatus(es) in accordance with thepresent invention include constitutions wherein a plurality of reactors12 comprising cylinder(s) 12 a and piston(s) 12 b belonging to suchcylinder(s) are provided. With such plural constitution, wood mealreaction products discharged from scavenging valve 12 c of first reactor12 might be sequentially transferred by way of passage switchingvalve(s) 12 g to second reactor 12 and any reactor(s) therebelow. Inaddition, reaction might again be repeated in like fashion at secondreactor 12. As was the case above, in the present case as well it willbe possible to achieve required reaction time in accordance with thetype of reactant, making it possible to carry out treatment efficientlyoverall even from the standpoint of time and even in situations wheretimes on the order of minutes are required before reaction(s) can besatisfactorily completed. Such action may be obtained in like fashion inthe context of constitutions wherein a plurality of the aforesaidrotary-type reactors 120, and/or centrifugal compressors 34, radialturbines 35, and/or other such turbo-type compressor-expanders and/orreactors are provided.

At the aforesaid drawings, 29 is an exhaust gas scrubber, exhaust gasproduced as a result of the aforesaid chemical reaction(s) and/orexhaust gas produced by boiler 11 being discharged to the atmospherefrom chimney 30.

Where the fluid medium is water, apparatus(es) in accordance with thepresent invention include constitutions, as shown in FIG. 10, providedwith oxidant supplier(s) 150 permitting sprayed introduction ofoxidant(s) into cylinder chamber(s) 12 a. Installation may be such that,from oxidant supplier(s) 150, this is directly coupled to reactor 12 byway of sprayer(s) 150 a and injector(s) 14 b. This makes it possible forsupercritical water oxidation reaction(s) to occur within cylinder 12 a,permitting oxidative decomposition of wood meal.

That is, adoption of a constitution wherein oxidant supplier(s) 150 ismade to spray will make it possible—in accordance with the principles ofthe supercritical water oxidation method (Supercritical Water OxidationMethod) applicable to supercritical water within high-temperature,high-pressure domains at or above approximately 374° C. and 218atmospheres—to cause gas, liquid, and/or slurry-like organicsubstance(s) to form a homogeneous phase with wood meal in supercriticalwater, causing occurrence of a combustive reaction and permittingcomplete combustion and decomposition without use of catalyst. Thismakes it possible for treatment to be carried out with an energyconsumption that is lower than is the case during treatment withconventional supercritical water, subcritical water, or pressurized hotwater.

Where the fluid medium is water, constitutions may, as shown in FIG. 11,be adopted for reaction apparatus(es) in accordance with the presentinvention such that they are provided with gasification apparatus(es)comprising gas-liquid separator(s) 230 or the like at location(s)permitting capture of gas component(s) of separated products fromcyclone separator 23. Gas component(s) produced therein are obtained bytreating wood meal and/or other such organic substance(s) withsupercritical water for long period(s) of time and causing occurrence ofdecomposition reaction(s). At such gasification apparatus(es),substance(s) being treated are such that only the water vapor in gasmixture(s) of water vapor and methane, hydrogen, carbon monoxide, carbondioxide, and/or other such gas(es) is liquefied by cooling at heatexchanger 231, permitting separation thereof by gas-liquid separator230, located at a stage subsequent thereto, into water and into methane,hydrogen, carbon monoxide, carbon dioxide, and/or other such gas(es)resulting from decomposition. This is because, at normal pressure,whereas the boiling point of water is 100° C., that of methane is −182°C., that of hydrogen is −253° C., that of carbon monoxide is −191° C.,and that of carbon dioxide is −78° C.; which is to say that all of thelatter boil at temperatures very much lower than is the case for water.Thermal energy produced during liquefaction of water vapor may be usedto heat boiler supply water E at heat exchanger 231. Furthermore, waterresulting from separation at gas-liquid separator 230 may be once againreturned to the boiler.

Reaction apparatus(es) in accordance with the present invention mayemploy any of various organic-type substance(s) as reactantsubstance(s), including—in addition to wood—biomass feedstock(s)including municipal refuse; discarded tire(s), coal and/or other suchcarbon-containing substance(s); methanol and/or other suchlow-molecular-weight alcohol(s) and fat(s) and/or oil(s); and also PETbottle(s) and/or other such high-molecular-weight polymer(s); PCB(s),R-series refrigerant(s), DXN(s) (dioxin(s)), and/or other suchhalogen-containing substance(s); and so forth.

Where the fluid medium is water, alcohol(s), and/or other such proticfluid(s), and where reactant substance is biomass feedstock(s) includingmunicipal refuse, biomass(es) may be hydrolyzed with supercritical waterand/or subcritical water to obtain glucose and/or other suchlow-molecular-weight sugar(s) and/or the like as product(s).

Furthermore, where reactant(s) is or are any substance(s) selected fromamong biomass feedstock(s) including municipal refuse, discardedtire(s), coal and/or other such carbon-containing substance(s), suchselected substance(s) may be decomposed with supercritical water and/orsubcritical water to obtain synthesized gas(es) including methane gas,hydrogen, carbon dioxide, and carbon monoxide. At such time, iftemperature of supercritical water is made extremely high, thermaldecomposition will proceed rapidly, producing the aforesaid synthesizedgas component(s) and causing same to be dissolved in water which is insupercritical state. By returning this to low temperature, because samebecome synthesized gas(es) and become flammable gas(es), this may alsobe used as methanol feedstock.

Where reactant substance(s) is or are waste cooking oil(s) and/or othersuch fat(s) and/or oil(s), these may be made to undergotransesterification reaction(s) using supercritical alcohol(s) and/orsubcritical alcohol(s), making it possible to obtain ester compound(s).

Where the fluid medium is water, alcohol(s), and/or other such proticfluid(s), and when reactant substance(s) is or are PET bottle(s) and/orother such polyester(s), these may be decomposed to terephthalic acid,ethylene glycol, and/or other such chemical precursor(s), which may thenbe recovered.

Where reactant(s) is or are PCB(s), R-series refrigerant(s), DXN(s)(dioxin(s)), and/or other such decomposition-resistanthalogen-containing substance(s), [these] may be decomposed untilrendered harmless. In such case, decomposition is sometimes carried outwith addition of oxygen and/or other such oxidant(s) and/or alkaliand/or the like.

Where the fluid medium is water, alcohol(s), and/or other such proticfluid(s), reaction apparatus(es) in accordance with the presentinvention may, as shown in FIG. 12, when product(s) obtained bydecomposition of biomass(es) is or are glucose and/or other suchlow-molecular-weight sugar(s) such as was described above, be such thatprovision of ethanol fermentor(s) 232 at location(s) behind gas-liquidseparator 26 makes it possible, due to supercritical water and/orsubcritical water therein, to cause glucose and/or other suchlow-molecular-weight molecule(s) obtained by saccharification ofhigh-molecular-weight molecule(s) to be efficiently converted intoethanol. That is, water-soluble component(s) of product(s) at gas-liquidseparator 26 are introduced into ethanol fermentor 232, and ethanol isproduced as a result of action of yeast(s), colon bacillus or bacilli,and/or other such microorganism(s). Accordingly, in such a case, it ispossible to obtain ethanol more efficiently and with less consumption ofenergy than would be the case with conventional treatment apparatusesemploying supercritical water, subcritical water, hot water, or thelike. Furthermore, where water and/or other such protic fluid(s) insupercritical and/or subcritical state(s) is or are used to carry outsaccharification treatment, in contrast to times on the order of secondsor less for supercritical water and times on the order of anywhere fromseveral minutes to several seconds for subcritical water, because thetime required for carrying out such treatment would be several tens ofhours with enzymatic saccharification, extremely long treatment timesbeing required, the method of using supercritical water and/orsubcritical water to carry out saccharification makes it possible fortreatment to be carried out in extremely brief period(s) of time.

Where the fluid medium is water, alcohol(s), and/or other such proticfluid(s), as shown in FIG. 13, a constitution may be adopted wherein,instead of the aforesaid ethanol fermentor(s) 232, ABA fermentor(s) 233is or are provided at location(s) permitting introduction thereinto ofwater-soluble component(s) of product(s) obtained. At ABA fermentor 233,product(s) introduced thereinto may be converted as far as acetone,butanol, and ethanol. This permits ABA fermentation to be carried out.Reaction apparatus(es) in accordance with the present invention make itpossible to obtain acetone, butanol, and/or ethanol more efficiently andwith less consumption of energy than would be the case with conventionaltreatment apparatuses employing supercritical water, subcritical water,hot water, or the like.

Where the fluid medium is water, alcohol(s), and/or other such proticfluid(s), reaction apparatus(es) in accordance with the presentinvention may, as shown in FIG. 14, be such that provision of methanefermentor(s) 234 at location(s) behind gas-liquid separator 26 makes itpossible, due to supercritical water and/or subcritical water therein,to cause glucose and/or other such low-molecular-weight molecule(s)obtainable by breaking down high-molecular-weight molecule(s) intolower-molecular-weight molecule(s) to be efficiently converted intomethane gas. That is, product(s) broken down into lower-molecular-weightmolecule(s) by supercritical and/or subcritical fluid(s) is made toundergo conversion as far as methane gas due to action of methanefermentation microorganism(s) within methane fermentor 234. In such acase, it is possible to obtain methane gas more efficiently and withless consumption of energy than would be the case with conventionaltreatment apparatuses employing supercritical water, subcritical water,hot water, or the like; and in addition, it is moreover possible tocarry out treatment and obtain methane gas in much shorter time(s) andmuch more rapidly than would be the case with methods not employingsupercritical water and/or subcritical water.

Next, a first working example of reaction apparatus 10 for organicand/or other substance(s) employing supercritical fluid(s) which isassociated with the present invention will be described. This reactionapparatus 10 uses water as fluid.

At compressor-expander 12, where water vapor is to be compressed toobtain supercritical water, and reaction of reactant substance(s) withsupercritical water is to be carried out, pressure at the conclusion ofcompression must be greater than or equal to the critical pressure of22.1 MPa and temperature at such time must be greater than or equal tothe critical temperature of 374° C. Where reactant substance is woodmeal and this is to be hydrolyzed to obtain glucose and/or other suchlow-molecular-weight sugar(s), it is known that the higher the pressureat the conclusion of compression the more it will be possible tosuppress overdecomposition of product component(s), and furthermore,that the higher the temperature at such time the greater will be thereaction rate.

With such facts in mind, 25 MPa and 410° C. were therefore respectivelyselected as pressure and temperature to be reached by water vapor as aresult of compression. Here, assuming, based upon consideration of thelimit where the amount of wood meal is made small relative to the amountof water, that the effect thereof can be ignored, and moreover assumingthat there is no thermal transfer between water vapor and cylinderduring compression and so forth, the foregoing target point beingreached due to the change in entropy, the state of the wet vapor whichwould need to exist at the time that compression is initiated wasdetermined mathematically. Thermodynamic data for water and vapor isbased on Japan Society of Mechanical Engineers Steam Tables (1980).

Specific entropy s at the target point was first determined, permittingdetermination of dryness x such as would cause specific entropy to beequal to the target specific entropy based on the difference (s″−s′)between specific entropy s″ of saturated vapor and specific entropy s′of saturated water at the pressure assumed to exist prior tocompression. The table in FIG. 18 shows results calculated for asituation where the pressure of the wet vapor prior to compression is 3MPa and for the state existing at the target point.

As is clear from the results shown in this FIG. 18, saturationtemperature of wet vapor at 3 MPa is 234° C., and a dryness x of 75.2%is needed to obtain a specific entropy equal to the specific entropy atthe target point. Once dryness x has been determined, it is possible todetermine specific volume v and density 1/v of wet vapor based on thedifference (v″−v′) between specific volume v″ of saturated vapor andspecific volume v′ of saturated water. Compression ratio ε, defined asthe ratio between specific volume v prior to compression and specificvolume v₀ at the target point, can also be determined.

Based on FIG. 18, compression ratio ε being 7.3, if the volume withinthe cylinder prior to compression is compressed to 1/7.3 thereof it willbe possible to achieve the target supercritical water state. If it canbe assumed that the effects of reaction are small enough to be ignoredand that changes are isoentropic, then, after reaching the target point,expansion will proceed by virtue of the crank mechanism, volume withinthe cylinder reaching a maximum, and following expansion the same statewill be assumed as existed prior to compression. Note that with a watervapor pressure of 3 MPa prior to compression, this can also be used forexplosive disintegration of that saturated water in order to facilitatereaction of wood meal feedstock. Furthermore, if the pressure prior tocompression is very much greater than 3 MPa, then there is a possibilitythat it will no longer be possible to completely stop the reaction dueto the fact that saturation temperature is high.

Next, assuming that only saturated vapor is delivered to the interior ofthe cylinder prior to initiation of compression and that wood mealserving as reactant substance is sprayed together with cold water, theamount of cold water necessary to achieve a satisfactory and homogeneousdistribution of wood meal within the cylinder and to at the same timesuppress unwanted progress of reaction(s) during compression wasdetermined using the same conditions as above. To achieve the sametarget-point supercritical water state as for wet vapor with homogeneousmixture of wood meal at the end of compression, it is sufficient to makethe specific enthalpy prior to compression the same value as that forwet vapor. Taking specific enthalpy of cold water to be h_(w)′, specificenthalpy of wet vapor prior to compression to be h_(s)′, specificenthalpy of saturated vapor at such time to be h_(s)″, and mass of coldwater corresponding to total mass of water and water vapor to be y, thefollowing relationship can be derived from such fact(s).y=(h _(s) ″−h _(s)″)/(h _(s) ″−h _(w)′)

Where temperature of cold water is 50° C. and pressure of vapor prior tocompression is 3 MPa, the required value can be determined to be y=0.183based on the foregoing Japan Society of Mechanical Engineers SteamTables (1980). That is, the amount of cold water injected therein shouldbe 18% of the total amount of water, and the balance should be injectedinto the cylinder in a saturated-vapor state.

While the change in state will in practice differ from the foregoingideal scenario due to the influence of various factors including amountof reactant substance, reaction, thermal transfer between water vaporand walls, and so forth, the amount of this difference is not all thatlarge, and even where discrepancy or discrepancies exist it will besufficient to add appropriate correction(s) to design conditions.

Next, the energy budget applicable to reaction apparatus 10 will bedescribed in comparison with a flow-type supercritical water reactionapparatus representing a conventional reaction apparatus. As shown inFIG. 15, at a flow-type supercritical water reaction apparatus, whichrepresents a conventional reaction apparatus, cold water A in which alarge amount of feedstock wood meal is dispersed is mixed withsupercritical water W_(b) which is at a temperature higher than targettemperature (e.g., 410° C.), causing the target supercritical waterstate to be attained, and rapid cooling of supercritical water withcooling water W_(c) causes reaction of wood meal to be terminated.

Below, the energy budget for the conventional flow-type supercriticalwater reaction apparatus at 25 MPa and 410° C., this having been chosenas the target point, is calculated. Specific enthalpy h₁₅₀ at 150° C. ish₁₅₀=647.7 kJ/kg, and at 410° C. this is h₁₄₀=2691 kJ/kg. In addition,at 550° C., h₅₅₀=3337 kJ/kg. Calculation indicates that, given asituation where cooling water at 150° C. is circulating, thetarget-point supercritical state will be achieved if 550° C.supercritical water is made to flow thereinto and mix therewith in anamount which is approximately 3.165 times the amount of the cold water(calculated from the specific enthalpy formula h₄₁₀ (1+a)=h₁₅₀+h₁₅₀a,where the amount of supercritical water at 550° C. mixed therewith per 1kg of cold water at 150° C. is akg). Design conditions were such thatthe supercritical water is thereafter cooled to 150° C. with cold water,stopping the reaction.

As described above, in the conventional apparatus, the fact that thereaction is terminated through addition of cold water means that anamount of supercritical water at 550° C. which is 3.15 times the amountof cold water, or h₅₀₅×3.165=10560 kJ/kg worth of energy, must bediscarded. Note however that a portion thereof may be used to heat coldwater at normal temperature to 150° C. Accordingly, as shown in FIG. 16,in a conventional flow-type supercritical water reaction apparatus, theenergy loss component β₁ is 9910 kJ/kg, this being 10560 kJ/kg lessh₁₅₀, or the 648 kJ/kg component.

On the other hand, the energy budget for reaction apparatus 10 of thepresent invention at 25 MPa and 410° C., this having been chosen as thetarget point, is calculated such that cold water at normal temperatureis heated to 3 MPa and 234° C., and this wet vapor is compressed bymeans of a reactive expander to achieve the target point (25 MPa and410° C.). Design conditions were such that the supercritical water isthereafter cooled by expansion to again become 234° C. Specific enthalpyof wet vapor of dryness 0.752 at 3 MPa and 234° C. is 2357 kJ/kg, and at410° C. this is h₄₁₀=2691 kJ/kg. From FIG. 17, it can be seen that, ofthe specific enthalpy of the wet vapor (2691 kJ/kg), almost all theenergy represented thereby is recovered, the small irreversible energyloss component(s) being attributable to irreversible changesaccompanying chemical reaction of wood meal; i.e., thermal transferbetween cylinder wall(s) and liquid within cylinder(s); friction ofpiston(s), crank mechanism(s); and other such minor portions thereof,and so forth.

The work of compression performed by the reactor, based on the specificinternal energy u and the relationship u=h−pv (h=specific enthalpy;p=pressure; v=specific volume), is 313 kJ/kg (thermodynamic data forwater and vapor is based on Japan Society of Mechanical Engineers SteamTables (1980)). While almost all of the work of compression is recoveredduring expansion; reaction, thermal losses, friction and the likemanifest themselves as irreversible loss components, such losscomponents being captured by the motive force generator. If the totallost work at the reactor and the motive force generator is taken to be28%, such irreversible mechanical loss components would representapproximately 122 kJ/kg. Based on the fact that these loss componentsare captured by the motive force generator, if the theoretical thermalefficiency of the motive force generator is taken to be 33%,approximately 370 kJ/kg worth of heat would be required at the motiveforce generator. Accordingly, the energy loss component β′ at thereactor and the motive force generator is 370 kJ/kg, which is not morethan 1/27 of the 9910 kJ/kg at the conventional flow-type reactionapparatus. Furthermore, while reaction apparatus 10 bears the load ofthe explosive disintegrator, because the energy associated with theexplosive disintegrator is the same for both reaction apparatus 10 andthe conventional flow-type reaction apparatus, it has been omitted fromenergy budget calculations.

As described above, energy loss components are very much smaller and theamount of energy consumed during operation is very much less withreaction apparatus 10 than is the case with the conventional flow-typereaction apparatus.

Where a fluid other than water is used at the reaction apparatus of thepresent invention, it will still be possible to cause this to assume asupercritical state. Examples of such fluids are carbon dioxide, nitrousoxide, Freon 12, Freon 13, ethane, ethylene, propane, propylene, butane,hexane, methanol, ethanol, benzene, toluene, ammonia, and so forth. Dataindicating critical conditions for these substances is indicated at FIG.19.

The present apparatus permits attainment of supercritical state(s) withwater, for which critical temperature and pressure are high. Based onthe data indicating critical conditions at FIG. 19, because conditionsof critical temperature and critical pressure for Freon 12 are lowerthan is the case for water, in the event that Freon 12 is used as fluidmedium it will be more than possible to achieve supercritical states inthe context of the apparatus of the present invention.

As a second embodiment of the present invention, where Freon 12 was usedas fluid s medium, taking temperature to be 130° C. and pressure to be4.9 MPa at the target-point state for Freon 12, calculation was carriedout for a situation where the pressure of wet vapor prior to compressionis 0.7 MPa, the results being shown in the table at FIG. 20.Thermodynamic data for Freon 12 is based on Japanese Association ofRefrigeration R12 Refrigerant Table of Thermal Property Values (1981).

Based on FIG. 20, as was done above where the fluid was water,compression pressure ε having been determined to be 6.4, if the volumewithin the cylinder is compressed to 6.4/1 of what it was prior tocompression it will be possible to achieve the target supercriticalfluid state. Moreover, after reaching the target point, expansionproceeds by virtue of the crank mechanism, volume within the cylinderreaching a maximum, and following expansion the same state is assumed asexisted prior to compression.

At reaction apparatus 10 of the present invention, the energy budget at4.9 MPa and 130° C., this having been chosen as the target point, issuch that Freon 12 at normal temperature is heated to 0.7 MPa and 40.0°C., and this wet vapor is compressed by means of a reactor to achievethe aforesaid target point, design conditions being such that thesupercritical fluid is thereafter cooled by expansion to again become40.0° C. In the present case as well, of the specific enthalpy of thewet vapor, almost all the energy represented thereby is recovered, thesmall irreversible energy loss component(s) being attributable toirreversible changes accompanying chemical reaction; i.e., thermaltransfer between cylinder wall(s) and liquid within cylinder(s);friction of piston(s), crank mechanism(s); and other such minor portionsthereof, and so forth. Thus, while the work of compression is recoveredduring expansion; reaction, thermal losses, friction and the likemanifest themselves as irreversible loss components, such losscomponents being captured by the motive force generator.

Even where the fluid is Freon 12, because energy loss components at thereactor and the motive force generator in the apparatus of the presentinvention are very much smaller than values therefor in a conventionalflow-type reaction apparatus, the amount of energy required to operatethe apparatus of the present invention is extremely small.

POTENTIAL FOR USE IN INDUSTRY

Because reaction apparatus(es) for organic and/or other substancesemploying supercritical fluid and/or subcritical fluid in accordancewith the present invention are constituted as described above, benefitssuch as the following are delivered thereby.

Because reaction apparatus(es) for organic and/or other substance(s)employing supercritical water and/or subcritical water in accordancewith the present invention comprise—by virtue of piston(s), rotary,and/or turbocompressor(s) and turbine(s)—means for compressing vapor(s)and obtaining supercritical fluid(s) and/or subcritical fluid(s), meansfor bringing such supercritical fluid(s) and/or subcritical fluid(s)into contact with organic substance(s) and/or other reactantsubstance(s) and causing occurrence of chemical reaction(s), and meansfor causing expansion and decompression of fluid(s) including product(s)produced as a result of such chemical reaction(s), as well as means forspraying reactant substance(s) together with liquid-like fluid(s) intoreactor(s), it is possible to cool and rapidly stop (freeze) reaction(s)of reactant substance(s) occurring at rapid rate(s) in high-temperature,high-pressure fluid(s) without use of low-temperature liquid(s) (coldwater in the case where the fluid is water).

By adjusting speed(s) of vertical motion of piston(s) and/or rotarymotion of rotor(s), and/or by adjusting volume(s) of reaction vessel(s)connected to turbine(s) and turbocompressor(s), it is possible tocontrol reaction(s) with a “resolution” which is such that reaction(s)occurring at rapid rate(s) in supercritical fluid(s), subcriticalfluid(s), and/or other such high-temperature, high-pressure fluid(s) aredivided into extremely brief period(s) of time.

These means are such that work performed by expansion during lowering oftemperature(s) and pressure(s) as a result of expansion of supercriticaland/or subcritical high-temperature, high-pressure fluid(s) to stopreaction(s) is again utilized as work for compression of vapor(s),permitting recovery of energy necessary for generation of supercriticaland/or subcritical high-temperature, high-pressure fluid(s). By makinguse of this recovered energy, it is possible to provide an apparatuswherein energy in chemical reaction(s) occurring in supercritical and/orsubcritical high-temperature, high-pressure fluid(s) is extremely high.

By adopting constitutions wherein passage switching valve(s) and/orother such open-/close-type member(s) are respectively provided atpassage(s) of introductive port(s) and scavenging valves(s) in reactionmechanism(s) of reciprocating-type and/or rotary-type reactor(s) andwherein treatment of reactant substance(s) can can be carried outcontinuously and repeatedly for fixed period(s) of time when suchopen-/close-type member(s) are closed, or constitutions wherein aplurality of reciprocating-type and/or rotary-type reactors areprovided, it is possible to achieve effective treatment time(s) even forsubstance(s) to be treated requiring treatment of on the order ofminutes. Displays it possible to efficiently improve reactionproductivity using a simple constitution. In particular, adoption of amultiple-acting constitution wherein volumes at which fluid vaporcompression is carried out by the aforesaid reciprocating-typecylinder(s) and piston(s) is carried out at both sides of piston(s)permits improvement in reaction efficiency.

While the foregoing reciprocating-type and rotary-type reactors make useof cyclical treatment wherein reaction of reactant substance(s) iscarried out in cyclical fashion, in the case of turbine-type reactors itis possible for reactant substance(s) to be supplied theretocontinuously and for chemical reaction thereof to be carried outcontinuously.

Where the fluid is water and/or other such protic fluid, if thesubstance to be treated is ligneous feedstock and/or other suchorganic-type biomass(es), such organic-type biomass(es) may be brokendown (solubilized) to produce lower saccharide(s) or the like. Moreover,by subjecting such low-molecular-weight compound(s) to ethanolfermentation, ABE fermentation, and methane fermentation, efficientconversion to gaseous component(s) and/or liquid component(s) which arecapable of being used as fuel or the like will be possible. Where suchgaseous component is, for example, methane gas, this might furthermorebe reused by supplying same to methanol synthesizing apparatus(es), gasengine(s), and/or the like.

1. A reaction apparatus for organic and/or other substance(s) employingsupercritical fluid(s) and/or subcritical fluid(s), comprising: areactor operative for compressing vapor(s) and obtaining supercriticalfluid(s) and/or subcritical fluid(s), for bringing supercriticalfluid(s) and/or subcritical fluid(s) into contact with organic matterand/or other reactant substance(s), for causing occurrence of chemicalreaction(s), and for causing expansion and decompression of the fluid(s)including product(s) produced as a result of chemical reaction(s), thereactor including cylinder(s) and piston(s) provided at such cylinder(s)and operative to sequentially actuate by operating such piston(s) tocause compression of fluid(s); operating the piston(s) in reversedirection(s) following the chemical reaction(s) of the reactantsubstance(s) to lower temperature(s) and pressure(s); removing, from thecylinder(s), fluid(s) including the produced product(s); and, deliveringnew charge(s) of vapor(s) to the cylinder(s), and explosivedisintegration apparatus(es) that rapidly depressurize reactantsubstance(s) while same is or are immersed in high-pressure saturatedfluid(s); organic substance(s) and/or other reactant substance(s) beingpulverized by such explosive disintegration apparatus(es) for use insaid reactor, wherein the reactor includes a primary actuator forenergizing the reactor and a secondary actuator operably connected tothe primary actuator, the secondary actuator energized by waste energyof the reactor and operative to assist the primary actuator inenergizing the reactor, wherein the secondary actuator is operablyconnected to the primary actuator by coupling together a first crankmechanism and a second crank mechanism, said first crank mechanisumbeing connected the primary actuator, and said second crank mechanismbeing connected to the secondary actuator, and wherein either or both ofsaid first crank mechanism and said second crank mechanism is a cammechanism.
 2. A reaction apparatus for organic and/or other substance(s)employing supercritical fluid(s) and/or subcritical fluid(s) accordingto claim 1 wherein operation of piston(s) causes vapor(s) to becompressed at only one side within cylinder(s).
 3. A reaction apparatusfor organic and/or other substance(s) employing supercritical fluid(s)and/or subcritical fluid(s) according to claim 1 wherein delivery of newcharge(s) of vapor(s) to cylinder(s) only involves saturated vapor(s) offluid(s), cold fluid(s) or saturated liquid(s) of fluid(s) beinginjected into cylinder(s) together with reactant substance(s) duringinitiation of compression by piston(s), in mid-compression, or followingconclusion of compression.
 4. A reaction apparatus for organic and/orother substance(s) employing supercritical fluid(s) and/or subcriticalfluid(s) according to any of claims 1, 2 and 3 wherein volume(s), atwhich compression of vapor(s) is carried out, formed by piston(s) andcylinder(s) are provided to either side of piston(s).
 5. A reactionapparatus for organic and/or other substance(s) employing supercriticalfluid(s) and/or subcritical fluid(s) according to claim 4 whereincompressor-expander(s) is or are provided to either side of piston(s),and injector(s) (feedstock spray apparatus(es)) is or are provided atrespective compressor-expanders.
 6. A reaction apparatus for organicand/or other substance(s) employing supercritical fluid(s) and/orsubcritical fluid(s) according to any of claims 1, 2 and 3 wherein wetvapor(s) of fluid(s) are compressed by one of volumes or sets ofvolumes, at which compression of vapor(s) is carried out, formed bypiston(s) and cylinder(s) and provided to either side of piston(s), theother of volumes or sets of volumes maintaining fluid vapor(s) at highpressure(s).
 7. A reaction apparatus for organic and/or othersubstance(s) employing supercritical fluid(s) and/or subcriticalfluid(s) according to any of claims 1, 2 and 3 wherein, at mechanism(s)comprising cylinder(s) and piston(s) provided at such cylinder(s), workof piston(s) is recovered.
 8. A reaction apparatus for organic and/orother substance(s) employing supercritical fluid(s) and/or subcriticalfluid(s) according to any of claims 1, 2, and 3 provided with means forcausing fluid(s) including product(s) obtained from chemical reaction(s)to be separated into saturated matter and saturated vapor(s) by cycloneseparator(s) and/or centrifugal separator(s).
 9. A reaction apparatusfor organic and/or other substance(s) employing supercritical fluid(s)and/or subcritical fluid(s) according to any of claims 1, 2, and 3wherein passage switching valve(s) and/or other such open-/close-typemember(s) are respectively provided at introductive port(s) andscavenging valves(s) in mechanism(s) comprising cylinder(s) and/or rotorchamber(s) and piston(s) for such cylinder(s) and/or rotor(s) for suchrotor chamber(s); and in addition, such open-/close-type member(s) aresuch as to allow setting of open and/or closed state(s) thereof, settingof such open-/close-type member(s) so as to cause closure thereof atfixed time interval(s) permitting supercritical treatment by suchmechanism(s) to be carried out continuously and in ongoing fashion. 10.A reaction apparatus for organic and/or other substance(s) employingsupercritical fluid(s) and/or subcritical fluid(s) according to claim 9wherein scavenger member(s) and member(s) introducing vapor(s) intorespective cylinder(s) and/or respective rotor chamber(s) inmechanism(s) comprising cylinder(s) and/or rotor chamber(s), as well aspiston(s) and/or rotor(s) for same, there being a plurality thereof, aresequentially coupled by way of passage switching valve(s) and/or othersuch open-/close-type member(s); permitting respective processesperformed by means for compressing vapor(s) and obtaining supercriticalfluid(s) and/or subcritical fluid(s), means for bringing supercriticalfluid(s) and/or subcritical fluid(s) into contact with organicsubstance(s) and/or other reactant substance(s) and causing occurrenceof chemical reaction(s), and means for causing expansion anddecompression of fluid(s) including product(s) produced as a result ofchemical reaction(s) to be carried out a plurality of times.
 11. Areaction apparatus for organic and/or other substance(s) employingsupercritical fluid(s) and/or subcritical fluid(s) according to any ofclaims 1, 2, and 3 wherein mechanism(s) comprising cylinder(s) and/orrotor chamber(s), as well as piston(s) for such cylinder(s) and/orrotor(s) for such rotor chamber(s), are such that a plurality thereofare provided.
 12. A reaction apparatus for organic and/or othersubstance(s) employing supercritical fluid(s) and/or subcriticalfluid(s) according to any of claims 1, 2, and 3 provided with oxidantspray apparatus(es) permitting sprayed introduction of oxidant(s) intohigh-pressure reaction vessel(s) present at cylinder(s), rotorchamber(s), and/or between turbocompressor(s) and turbine(s); introducedorganic substance(s) and/or other reactant substance(s) beingoxidatively decomposed while in supercritical state(s).
 13. A reactionapparatus for organic and/or other substance(s) employing supercriticalfluid(s) and/or subcritical fluid(s) according to any of claims 1, 2,and 3 provided with gasification apparatus(es) further separating, intogas component(s) and liquid component(s), saturated vapor(s) separatedfrom fluid mixture(s) of product(s).
 14. A reaction apparatus fororganic and/or other substance(s) employing supercritical fluid(s)and/or subcritical fluid(s) according to any of claims 1, 2, and 3wherein reactant substance(s) is or are biomass feedstock(s) includingmunicipal refuse; and product(s) is or are glucose and/or other suchlow-molecular-weight sugar(s) and/or the like obtainable throughdecomposition of biomass(es).
 15. A reaction apparatus for organicand/or other substance(s) employing supercritical fluid(s) and/orsubcritical fluid(s) according to any of claims 1, 2, and 3 whereinreactant substance(s) is or are any substance(s) selected from amongbiomass feedstock(s) including municipal refuse, discarded tire(s), coaland/or other such carbon-containing substance(s); and product(s) is orare synthesized gas(es) including methane gas, hydrogen, carbon dioxide,and carbon monoxide obtainable through decomposition of the aforesaidselected substance(s).
 16. A reaction apparatus for organic and/or othersubstance(s) employing supercritical fluid(s) and/or subcriticalfluid(s) according to any of claims 1, 2, and 3 wherein reactantsubstance(s) is or are PET (POLYETHYLENE TEREPHTHALATE) bottle(s) and/orother such high-molecular-weight polymer(s); and product(s) is or arehigh-molecular-eight-polymer-material feedstock substance(s).
 17. Areaction apparatus for organic and/or other substance(s) employingsupercritical fluid(s) and/or subcritical fluid(s) according to any ofclaims 1, 2, and 3 wherein reactant substance(s) is or are waste cookingoil(s) and/or other such fat(s) and/or oil(s); same being converted intofatty acid ester(s) by supercritical fluid(s) and/or subcriticalfluid(s).
 18. A reaction apparatus for organic and/or other substance(s)employing supercritical fluid(s) and/or subcritical fluid(s) accordingto any of claims 1, 2, and 3 wherein reactant substance(s) is or arePCB(s) (POLYCHLORINATED BIPHENYL(s)), R-series refrigerant(s), DXN(s)(dioxin(s)), and/or other such chlorine-containing substance(s);reactant substance(s) being decomposed and rendered harmless.
 19. Areaction apparatus for organic and/or other substance(s) employingsupercritical fluid(s) and/or subcritical fluid(s), comprising: areactor operative for compressing vapor(s) and obtaining supercriticalfluid(s) and/or subcritical fluid(s), for bringing supercriticalfluid(s) and/or subcritical fluid(s) into contact with organic matterand/or other reactant substance(s), for causing occurrence of chemicalreaction(s), and for causing expansion and decompression of the fluid(s)including product(s) produced as a result of chemical reaction(s), thereactor including cylinder(s) and piston(s) provided at such cylinder(s)and operative to sequentially actuate by operating such piston(s) tocause compression of fluid(s); operating the piston(s) in reversedirection(s) following the chemical reaction(s) of the reactantsubstance(s) to lower temperature(s) and pressure(s); removing, from thecylinder(s), fluid(s) including the produced product(s); and, deliveringnew charge(s) of vapor(s) to the cylinder(s); and explosivedisintegration apparatus(es) that rapidly depressurize reactantsubstance(s) while same is or are immersed in high-pressure saturatedfluid(s); organic substance(s) and/or other reactant substance(s) beingpulverized by such explosive disintegration apparatus(es) for use insaid reactor.
 20. A reaction apparatus for organic and/or othersubstance(s) employing supercritical fluid(s) and/or subcriticalfluid(s), comprising: a reactor operative for compressing vapor(s) andobtaining supercritical fluid(s) and/or subcritical fluid(s), forbringing supercritical fluid(s) and/or subcritical fluid(s) into contactwith organic matter and/or other reactant substance(s), for causingoccurrence of chemical reaction(s), and for causing expansion anddecompression of the fluid(s) including product(s) produced as a resultof chemical reaction(s), the reactor including cylinder(s) and piston(s)provided at such cylinder(s) and operative to sequentially actuate byoperating such piston(s) to cause compression of fluid(s); operating thepiston(s) in reverse direction(s) following the chemical reaction(s) ofthe reactant substance(s) to lower temperature(s) and pressure(s);removing, from the cylinder(s), fluid(s) including the producedproduct(s); and, delivering new charge(s) of vapor(s) to thecylinder(s); and ethanol fermentor(s) having colon bacillus or bacilliand yeast(s) into which liquid component(s) of glucose and/or other suchlow-molecular-weight sugar(s) and/or other such product(s) obtainedthrough decomposition of biomass(es) via said reactor is or areintroduced; sugar(s) introduced into such ethanol fermentor(s) beingconverted as far as ethanol by the aforesaid yeast(s), colon bacillus orbacilli , and/or the like.
 21. A reaction apparatus for organic and/orother substance(s) employing supercritical fluid(s) and/or subcriticalfluid(s), comprising: a reactor operative for compressing vapor(s) andobtaining supercritical fluid(s) and/or subcritical fluid(s), forbringing supercritical fluid(s) and/or subcritical fluid(s) into contactwith organic matter and/or other reactant substance(s), for causingoccurrence of chemical reaction(s), and for causing expansion anddecompression of the fluid(s) including product(s) produced as a resultof chemical reaction(s), the reactor including cylinder(s) and piston(s)provided at such cylinder(s) and operative to sequentially actuate byoperating such piston(s) to cause compression of fluid(s); operating thepiston(s) in reverse direction(s) following the chemical reaction(s) ofthe reactant substance(s) to lower temperature(s) and pressure(s);removing, from the cylinder(s), fluid(s) including the producedproduct(s); and, delivering new charge(s) of vapor(s) to thecylinder(s); and ABE fermentor(s) having ABE fermentationmicroorganism(s) into which liquid component(s) of glucose and/or othersuch low-molecular-weight sugar(s) and/or other such product(s) obtainedthrough decomposition of biomass(es) via said reactor is or areintroduced; sugar(s) introduced into ABE fermentor(s) being converted asfar as acetone, butanol, and ethanol by ABE fermentationmicroorganism(s).
 22. A reaction apparatus for organic and/or othersubstance(s) employing supercritical fluid(s) and/or subcriticalfluid(s), comprising: a reactor operative for compressing vapor(s) andobtaining supercritical fluid(s) and/or subcritical fluid(s), forbringing supercritical fluid(s) and/or subcritical fluid(s) into contactwith organic matter and/or other reactant substance(s), for causingoccurrence of chemical reaction(s), and for causing expansion anddecompression of the fluid(s) including product(s) produced as a resultof chemical reaction(s), the reactor including cylinder(s) and piston(s)provided at such cylinder(s) and operative to sequentially actuate byoperating such piston(s) to cause compression of fluid(s); operating thepiston(s) in reverse direction(s) following the chemical reaction(s) ofthe reactant substance(s) to lower temperature(s) and pressure(s);removing, from the cylinder(s), fluid(s) including the producedproduct(s); and, delivering new charge(s) of vapor(s) to thecylinder(s); and methane fermentor(s) having methane fermentationmicroorganism(s) into which gaseous component(s) of product(s) obtainedthrough decomposition of biomass(es) via said reactor is or areintroduced; sugar(s) from product(s) introduced into methanefermentor(s) being decomposed as far as methane gas by methanefermentation microorganism(s).